Aldehyde cellulose products and the process of making same



Patented Jan. 28 1947 UNITED STATES PATENT OFFICE ALDEHYDE CELLULOSE PRODUCTS AND THE PROCESS OF MAKING SAME John B. Rust, West Orange, N. J., Montclair Research Corporation,

of New Jersey assfgnor to a corporation No Drawing. Application March 23, 1944, Serial No. 527,828

' washand laundering-fast cellulose textile sizes;

It is a further object to provide cellulose derivatives which may be dissolved in alkali solution and spun into fibers in a suitable precipitating bath for the production of artificial silk or precipitated in the form of film or foils. It is also an object of this invention to provide paper sizing and modifying agents.

Othenobiects and advantages will become apparent from the more detailed description of the invention given hereinafter. Such detailed description should not be construed as limiting, but only by way of explanation and illustration, since numerous variations may be made by those skilled in the art without departing from the scope and spirit of the present invention.

The derivatives of the present invention may be formed by the reaction of an alkali cellulose derivative, as for instance, soda cellulose, potash cellulose, lithium cellulose, quaternary ammonium cellulose and the like with alpha-beta unsat urated aldehydes. The reaction may be efiectcd in the cold, in some instances, and in others by the application of heat.

As instances of aldehydes which may be used in the process of the present inventinn are acrolein,'methacrolein, ethacrolein, 2-ethyl hexenal, crotonaldehyde. and the like. I may first-react cellulose with sodium hydroxide, for instance, to form soda cellulose. After aging the soda cellulose to a satisfactory degree, as explained below, it is mixed with cooling with the alpha-beta unsaturated aldehyde. Reaction is efiected either in the cold or the reaction mixture is allowed to warm up and further heating applied. I prefer to employ aldehydes which are substituted in the alpha-position since they are not capable of undergoing aldol condensation and hence are nonresinifying with alkalies. However, I may use unsubstituted aldehydes andwork with diluents or at low temperatures to obviate or reduce resinifying reactions. Thus, the aldehydes of the present invention may be represented by:

R1CH=(|3CHO where R and R may be alkyl, aryl, alkaryl, aral- 11 Claims. (Ci.106-197) kyl, olefinyl, alkynyl, and the like or hydrogen. In the reaction of the present invention, it is suggested that the following reaction may occur. Representing cellulose as Cell-OH:

Cell-OH R'C}I=CCHO Cell-O--CHCHCHO Since rather strong alkaline conditions are employed, it is suggested that the aldehyde reaction product may, undergo to some extent the Cannizzaro reaction and a mixture of the above substituted aldehyde and the following is obtained: r r cen -ocrkcnomon, Cell-O-CH-CH-OOOH The above is given by way of possible explanation only and should not be construed as limting ative on the textile.

since I do not wish to be limited by any theoretical' explanation of the reaction of the present invention.

The cellulose derivatives are soluble in alkalies, with cooling or not, according to the number and kind of substituted groups. Thus. I may make a derivative which is insoluble in alkali atordinary temperatures but which is readily soluble by cooling the alkali suspension to about 0 C. Such solutions are valuable as textile sizing agents. The solutions, usually of about 1% to 10% strength, are applied to cotton, linen, or rayon goods on a padder, squeezed, dried and coagulated by using a solution of an acid, acid salt, or a precipitating concentrated salt solution. The treated textile is washed thoroughly after coagulating and then dried. A firm hand is imparted to the fabric which is resistant to laundering and the ordinary cleansing agents. The finish may be applied at practically any convenient stage of processing such as before kier boiling, before dyeing and the like.

Since the derivatives of the present invention contain aldehyde groups they may be caused to undergo further reaction, as for instance with aldehydes, 'acids, phenols, amines and ammonia, hydroxylamine, hydrazine, hydrogen cyanide and the like. Thus, if used as a sizin material, the derivatives of the present invention may be subjected to heat after coagulation which causes a further reaction of the aldhyde group with subsequent cross-linking and curing of the deriv- On the other hand a textile sized with the derivatives of the present invention may be treated withformaldehyde or other aldehyde in order to effect curing and fixation. Still further, the textiles sized with the derivatives of thisjnvention may be treated with ammonia, amines, or other nitrogenous derivatives reactive with aldehydes. Such treated sized x textiles are then much more receptive to dyestuils capable of dy ing wool, silk, hair and the I like.

Cellulose in its various forms may be used in the present invention: However, 'after forming the alkali orquaternary ammonium cellulose, I

prefer to age it to secure some controlled deara 7. u dation until the desired viscosity is obtained. The

ture. Afterwards the reaction mixture is acidilied, whereby the product is coagulated and can be filtered, washed and dried. The dried product is capable of dissolving in dilute aqueous alkalles to form a homogeneous solution useful particula'rly' as a wash-fast size for fabrics.

The following examples are given to illustrate the products and processes of the present invention. All proportions are in parts by weight.

Example 1.84 parts of soda cellulose, containing 15.6% of cellulose and 84.4% of 80% sodium'hydroxide solution and a ed for 16 hours.

dichloride. carbon tetrachloride, benzene, ethyl ether, heptane and the like. when making the alkali cellulose, concentrations of from 15% to 50% of alkali may be used although greater or lesser concentrations can be employed. I usually prefer to employ concentrationsof about 80% to 40%. This is also true of the quaternary ammonium hydroxides. When using these latter materials solution of the cellulose sometimes occurs. In such cases, the solutions may be diluted with alkali metal hydroxide solutionsbefore re action. Such quaternary ammonium hydroxides ,may-be trimethyl benzyl ammonium hydroxide.

tetraethyl ammoniiun hydroxide. diethyl dipropyl ammonium hydroxide, 'diethyl piperidinlum hydroxlde, methyl pyridinlum hydrox e and the like. I I

The proportions of reactants may be varied within very large limits of. for instance, from 5% to about 100% of the cellulose. For several reasons it may be desirable to use an excess of unsaturated aldehyde. For instance, in some cases a Cannizzaro reaction occurs very readily, or a resinification reaction occurs with subsequent impoverishment of the mixture of the aldehyde. n the other hand a greater proportion of unsaturated aldehyde may he used to accelerate the reaction. which may. then be terminated before completion, if desired.

1 As well as utilising the aldehydes given above. I may also use alpha-beta unsaturated aldehydes containing other negative substltuents as for instance alpha-cyano acrclein, alpha-carbethoxy acrolein, beta-cyano acrolein; beta-carbethoxy acrolein, alpha-acetyl acrolein. beta-acetyl acrolein, alpha-beta-diaoetyl acrolein, maleic diaidehyde, and the like. These may be represented by the general formula n a on=ocno where besides being alkykaryl, etc., It and B may were mixed with 20 parts of crushed ice and 10 parts of methacrolein. The mixture was homosenized and allowed to come to room temperatures It was then brought to 30 C. for 3 hours.

. The mixture formed a solution when diluted with water. The derivative was coagulated by addition of HCl solution, washed with water and acetone and dried. This derivative was a white powdery substance and was readily soluble at room temperature in 5% to sodium hydroxide solution to give a thin solution of 5% methacrolein cellulose. 2

Example 2.-86.5 parts of soda cellulose, containing parts of cellulose, and 51.5 parts of 33%% sodium hydroxide solution, were mixed' with 10 parts of snow and 5 parts of methacro- 1am. The mixture was thoroughly homogenized and parts of water added. The mixture was allowedto come to room temperature over a one hour period, then reacted for 1 hour at 50: C. A

white product was obtained which was acidified with acetic acid, and washed thoroughly with water and acetone and dried. A white fibrous material was formed which was soluble in sodium hydroxide solutions on cooling.

Example 3.--A solution of the methacroleincellulose of Example 2 was made by mixing 4 parts of methacrolein-celiulose with 80 parts of 33% sodium hydroxide solution, '10 parts of water and 100 parts of crushed ice. The solution was clear and relatively non-viscous. A piece of cotton broadcloth was immersed in the solution, the excess solution squeezed out and the textile dried. The cloth was then passed through a bath containing 10% sulfuric acid and finally washed and dried. 'A ilrm hand was imparted to the cloth. This was not diminished to any substan tial extent upon laundering.

Example 4.--64 parts of soda cellulose, containing 10 parts of cellulose and 54 parts of sodium hydroxide solution, were mixed with 20 parts of crushed ice and 10 parts of crotonaldehyde. The mixture was allowed to warm to room temperature and was then heated to I C. for 2 hours. A dark red mixture was ob- 40%) aqueous solution of an alkali such as sodium hydroxide to form alkali cellulose. The amount of alkali amounts to from 8 to about 8 moles per CcHmOs group of cellulose. To this mixture is then added from 5% to about 100% (based on dry cellulose) 01 an alpha-beta unsaturatedaldehyde as above defined and reacted for a period from i to about 5 hours. The reaction temperature is between ice temperature and boiling, higher temperatures being employed when a degraded product (that is, one producing a lower viscosity) is desired, but in any case it is desirable to start the reaction at ice temperatained which when neutralized, washed with water and acetone and dried, was a light yellow powder. The crotonaidehyde-cellulose was soluble in 10% sodium hydroxide solution with cooling to give a viscous yellow solution of 5% strength.

Example 5.7'l parts of soda cellulose, containing 20 parts of cellulose and 5'7 parts of 30% sodium hydroxide solution, were mixed with 20 parts of 2-ethyl-3-propyl acrolein. The mixture was heated at C. for 2% hours, then neutralized, washed with water and acetone and dried. A white fibrous mass was obtained which was soluble in 10% sodium hydroxide solution with cooling.

Example 6.35 parts of soda cellulose, containing 10 parts of cellulose and 25- parts of 33 sodium hydroxide solution, were mixed M suse with parts-oi ice and then 50 parts oi a 10% solution of acrolein in dioxan were mixed in and homogenized. The mixture was allowed to come to room temperature for 1 hour and then at 40 60 C. for 1 hour. The reaction mixture was-neutralized with acetic acid, washed with water and acetone and dried. A white fibrous derivative was obtained which was soluble in 10% sodium hydroxide solution with cooling to giv a viscous solution of 5% strength. 7

I claim:

1. The process of making an aldehyde-cellu lose product which is soluble in dilute aqueous alkali solutions, which consists in reacting an alpha-beta unsaturated aldehyde with alkali cellulose, coagulating the reaction mixture by aciditying it, and recovering the reaction product by filtering, washing and drying the same: the aldehyde being represented by the formula where R and R are selected from the class consisting of hydrogen and alkyl, aryl, aralkyl, oleflnyl, alkynyl, cyano, carboxy, carbalkoxy, aldehydo and acyl groups.

2. The process-0t making an aldehyde-cellulose.

product which is soluble in dilute aqueous alkali 1 solutions, which consists in allowing cellulose to react with a to aqueous solution or.

acidifying the reaction mixture and recovering V the reaction product by filtering, washing and drying same; the aldehyde being representedby the formula where R and R are selected from the class consisting of hydrogen and alkyl, aryl, aralkyl, olefinyl, alkynyl, cyano, carbon, carbalkoxy. aldehydo and acyl groups.

3. Process 01' making an aldehyde-celhliose product which is soluble in dilute aqueous alkali solutions, which consists inreacting methacrolein and alkali cellulose, acidifying the reaction mix- .ture and recovering the reaction product by filtering, washing and drying the same.

4. Process of making an aldehyde-cellulose product which is soluble in dilute aqueous alkali solutions, which consists in reacting 2 ethyl-3- propyl acrolein, and alkali cellulose. acidifying the reaction mixture tion product by filtering, washing and drying the.

6 and recovering the reacsame.

5. Process of making an aldehyde-cellulose product which is soluble in dilute aqueous alkali solutions, which consists in reacting acrolein and alkali cellulose, acidifying the reaction mixture and recovering the reaction product by filtering, washing and drying the same.

6. An aldehyde-celluloseproduct soluble in dilute aqueous alkalies, consisting of the acidcoagulated', washed and dried reaction product of an alpha-beta unsaturated aldehyde and alkali cellulose; the aldehyde being represented by the formula where R and R are selected from the'classeonsisting oi-hydrogen and alkyl, aryl. aralkyl, oleilnyl, alkynyl, cyano, carboxy. carbalkoxy, aldehydo and acyl groups.

"I. An aldehyde-cellulose product soluble in dilute aqueous alkalies, consisting of the acidcoagulated, washed and dried reaction product of an alpha-beta unsaturated aldehyde and soda cellulose, the soda cellulose being prepared with a 30% to about40% aqueoussodium hydroxide solution with the amount oi sodium hydroxide equalto from 3 to about 8 moles NaOH per- CsHi'oOa group of cellulose, and the amount of "unsaturated aldehyde being from 5% to about oi. the cellulose; the aldehyde being represented by the formula where R and R are selected from the class con sisting 0! hydrogen and alkyl, aryl, aralkyl, oleiinyl, alkynyl. cyano, carboxy, carbalkoxy, aldehydo and acyl groups.

8. An aldehyde-cellulose product soluble in dilute aqueous alkalies, consisting of the acidcoagulated, washed and dried reaction product of methacrolein and alkali cellulose.

9. An aldehyde-cellulose product soluble in dilute aqueous alkalies, consisting. of the acidcoagulated, washed and dried reaction product oi'z-ethyl-ii-propyl acrolein and alkali cellulose.

10. An aldehyde-cellulose product soluble in dilute aqueous alkalies. consisting of the acid- 'coagulated, washed and driedreaction product oi acrolein and alkali cellulose.

11. a solution of the aldehyde-cellulose prodaqueous sodium hydroxide not of claim 6 in dilute solution.

JOHN a. near. 

